CN103394368A - Light oil type hydrocracking catalyst with composite molecular sieve as well as preparation method and application thereof - Google Patents
Light oil type hydrocracking catalyst with composite molecular sieve as well as preparation method and application thereof Download PDFInfo
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- CN103394368A CN103394368A CN2013103126789A CN201310312678A CN103394368A CN 103394368 A CN103394368 A CN 103394368A CN 2013103126789 A CN2013103126789 A CN 2013103126789A CN 201310312678 A CN201310312678 A CN 201310312678A CN 103394368 A CN103394368 A CN 103394368A
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- molecular sieve
- composite molecular
- molecular screen
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- light oil
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Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 69
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 20
- 238000005336 cracking Methods 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 238000010335 hydrothermal treatment Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000000295 complement effect Effects 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- -1 hexafluorosilicic acid ammonium salt Chemical compound 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002803 maceration Methods 0.000 claims description 2
- 239000000320 mechanical mixture Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000001935 peptisation Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003795 desorption Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002101 lytic effect Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a light oil type hydrocracking catalyst with a composite molecular sieve. The hydrocracking catalyst comprises the composite molecular sieve consisting of a modified Y-molecular sieve and a modified ZSM-23 molecular sieve, a carrier composed of micropore aluminum oxides, and a hydrogenation activity component composed of a VIB group metal and a VIII group metal. The hydrocracking catalyst is characterized in that the composite molecular sieve comprises the modified Y-molecular sieve and the modified ZSM-23 molecular sieve, and the Y-molecular sieve is modified and dealuminized, so that heat stability and hydrothermal stability are stably enhanced, the hydrophobicity is enhanced, the absorption and desorption properties of the molecular sieve are improved, and the catalyst achieves a high catalytic cracking property. The pore passages of the modified SM-23 molecular sieve are unobstructed, the number of the acid sites is small, the isomerism property is outstanding, and the octane value of the molecular sieve is increased because of light naphtha components. The modified Y-molecular sieve and the modified ZSM-23 molecular sieve are mixed and used according to a formula ratio of the hydrocracking catalyst, so that both the cracking activity and the isomerism property are considered, and the final catalyst achieves an ideal catalytic effect.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof and application, particularly a kind of hydrocracking process process that is applicable to produce light ends oil comprises light oil type hydrogen cracking catalyst of composite molecular screen and its preparation method and application.
Background technology
At present, worldwide petroleum resources are more and more nervous, and the crude oil of existing oil field output also becomes and heavily becomes bad.And along with the development of society, people grow with each passing day to the demand of light-weight fuel oil, and environment is day by day harsh to the requirement of fuel oil.The quality and quantity of oil time processing all can not meet people's needs, and by the secondary operations of oil, the light Fuel that heavy distillate is converted into high-quality has not only been utilized limited petroleum resources fully, and has alleviated the market demand of light ends oil.Hydrocracking technology is strong to adaptability to raw material, production decision is flexible, product quality is high, it is one of Main Means of oil secondary operations, the light naphtha fraction super-low sulfur that it is produced, low alkene and low aromatic hydrocarbons, the blend component of high-quality clean gasoline, but the light naphthar octane number that hydrocracking is at present produced＜80 (RON).The hydrocracking technology key is hydrocracking catalyst, the light oil with high yield product just to require light oil type hydrogen cracking catalyst to have higher activity.
Y zeolite has had the many decades time as the acidic cleavage component of hydrocracking catalyst, so far still in a large amount of uses.Because it is found that Y molecular sieve is through dealuminzation, improve its skeleton Si/Al than the variation that can bring a series of structures and chemical property, comprise that structure cell contraction, the reduction of surface acid center concentration, acid site strength increase, acid site distribution disperse, produce simultaneously secondary mesopore etc.Structure cell shrinks, and heat and hydrothermal stability just strengthen; Absorption property changes, and hydrophobicity strengthens; Part of hydroxyl is removed, and sour density and acid strength change; Produce secondary pore, effective aperture changes, and improves the adsorption and desorption performance of molecular sieve., by suitable modification, make Y molecular sieve have higher acid amount and suitable acidity distribution, thereby make catalyst obtain higher catalytic pyrolysis performance in a word.
ZSM-23 molecular screen is a kind of mesopore, high-silica zeolite, has the topological framework of MTT structure.Comprise simultaneously five-membered ring, hexatomic ring and ten-ring in the matrix topology of ZSM-23 molecular screen, but without the intersection pore passage structure of similar MFI structure molecular screen.It is mutual not crosslinked parallel duct by the one-dimensional channels that ten-ring forms, and free diameter is 0.56 * 0.45nm, with the 0.56 * 0.54nm of ZSM-5 in catalytic reaction, with 0.55 * 0.53nm duct, compares, and the pore size of ZSM-23 is slightly little.Due to the pore passage structure of ZSM-23 molecular screen uniqueness, show excellent isomery performance in catalytic reaction, have well selective.
The patent No. provides a kind of light oil type hydrogen cracking catalyst and preparation method thereof for 94117759.9 patent of invention, catalyst contains low-Na and high-Si Y-type molecular sieve (pressing the CN90102645.x preparation), (boehmite: three water contents are less than 3w% for little porous aluminum oxide, pore volume 0.48～0.60ml/g, specific area 180～340m
2/ g), tungsten oxide and nickel oxide; Its preparation method is extruded moulding after low-Na and high-Si Y-type molecular sieve mixes with the aperture aluminium oxide, and article shaped is high-temperature process under ammonia-water vapour atmosphere, and with the mixed solution dipping of tungstenic, nickel, dry, roasting, obtain the catalyst finished product finally.Catalyst is processed vacuum distillate and is had higher activity, anti-nitrogen performance that light oil is selective and high under hydrocracking condition.But it is on the low side that liquid is received, and the octane number of naphtha is not high.
Publication number is US4, and 672,048 patent of invention discloses a kind of light oil type hydrogen cracking catalyst, and molecular sieve used is LZ-210, its SiO
2/ Al
2O
3Mol ratio is preferably 11～15, and its preparation method is: ammonium hexafluorosilicate is processed NH in acidic buffer solution
4The NaY molecular sieve, fluorine-containing accessory substance enters liquid phase, and in product LZ-210, sodium and solution reach balance,, so the LZ-210 sodium content is higher,, generally in the 0.5w% left and right,, if obtain low sodium content, also need further ammonium exchange.In addition, easily contain fluoride in molecular sieve, thereby reduce the activity of catalyst.The method of catalyst preparation is the first hydrothermal treatment consists of LZ-210, then ammonium exchange, then the adhesive moulding, drying, the roasting that make with aluminium oxide, soak metal.The catalyst of this technology preparation has the selective and anti-nitrogen performance of higher light oil, and the activity of catalyst is not very high.
Summary of the invention
The present invention is directed to the deficiency of prior art, provide that a kind of lytic activity is high, light oil selectively good, liquid receive hydrocracking process process that high and high being applicable to of light naphthar octane number produce light ends oil comprise light oil type hydrogen cracking catalyst of composite molecular screen and its preparation method and application.
Technical scheme of the present invention is: a kind of light oil type hydrogen cracking catalyst that contains composite molecular screen, the composite molecular screen that forms take modified Y molecular sieve and modified ZSM-5-23 molecular sieve is as acidic components, take group VIB metal and group VIII metal as the hydrogenation activity component, the modified Y molecular sieve SiO in described composite molecular screen
2/ Al
2O
3Mol ratio is 10～15, specific area 700～850m
2/ g, pore volume 0.40～0.50ml/g, lattice constant 2.445～2.455nm, relative crystallinity 〉=90%, Na
2O content≤0.15wt%, infrared total acid are 0.5～1.2mmol/g, the modified ZSM-5-23 molecular sieve SiO in described composite molecular screen
2/ Al
2O
3Mol ratio is 50～70, specific area 260～450m
2/ g, pore volume 0.30～0.45ml/g, infrared total acid is generally 0.1～0.25mmol/g.
Preferably, in described composite molecular screen, the weight ratio of modified Y molecular sieve and modified ZSM-5-23 molecular sieve is 75:25-95:5.
Preferably, described little porous aluminum oxide is boehmite, and its pore volume is 0.45～0.55ml/g, and specific area is 180～380m
2/ g.
Preferably, described group VIB metal is tungsten or molybdenum, and group VIII metal is nickel or cobalt.
Preferably, described composite molecular screen content is 30～60wt%, and aperture aluminium oxide 10～26wt%, group VIB metal be take oxide content as 20～26wt%, and group VIII metal is take the content of oxide as 3～7wt%.
The above-described preparation method who contains the light oil type hydrogen cracking catalyst of composite molecular screen comprises the following steps:
With composite molecular screen and the adhesive that made by little porous aluminum oxide and dilute nitric acid solution peptization carry out mechanical mixture, roll, moulding, then dry, roasting, obtain catalyst carrier, and carrier floods with the maceration extract that contains tungsten nickel, then dry, roasting, make finished catalyst.
Preferably, in described composite molecular screen, modified Y molecular sieve is to make by the following method:
Sodium type Y molecular sieve carries out ion-exchange with the aqueous solution of ammonium salt, prepares Na content with Na
2O weighing scale content is less than 3.0% ammonium type Y molecular sieve;
Ammonium type Y molecular sieve hexafluorosilicic acid ammonium salt solution dealumination complement silicon, the silica alumina ratio of raising molecular sieve, the sieve sample after dealumination complement silicon separates with accessory substance, and sieve sample is carried out suction filtration, washing and dry;
Sieve sample to drying carries out hydrothermal treatment consists;
Sieve sample after hydrothermal treatment consists exchanges with ammonium salt solution, and ammonium salt solution transfers to pH=2.5～5.5 with acid.
Preferably, described reaction condition with hexafluorosilicic acid ammonium salt solution dealumination complement silicon is: the concentration of hexafluorosilicic acid ammonium salt solution is 0.5～1.2M, and system temperature is controlled at 70～120 ℃, and the dealumination complement silicon time is 0.3～5.0 hour.
Preferably, described sieve sample and separation of by-products adopt sedimentation-separation technology to isolate zeolite product and accessory substance, and the sedimentation time is 0.1～1.0 hour.
Preferably, 500～750 ℃ of the temperature of described Y molecular sieve hydrothermal treatment consists, water vapour pressure 0.01～0.50MPa, 0.5～5.0 hour time.
Preferably, the sieve sample after described hydrothermal treatment consists is with in the ammonium salt solution exchange step, and ammonium salt is one or several in ammonium chloride, ammonium nitrate, ammonium sulfate, and the acid of regulating pH is hydrochloric acid, nitric acid or sulfuric acid.
Preferably, in described composite molecular screen, the condition of described HZSM-23 zeolite-water heat treatment is: 400～600 ℃ of temperature, water vapour pressure 0.01～0.20MPa, 0.5～3.0 hour time.
The above-described application that contains the light oil type hydrogen cracking catalyst of composite molecular screen, in hydrocracking process, be used for the hydrocracking process of voluminous light ends oil.
Preferred reaction process condition is: reaction temperature is 360～380 ℃, stagnation pressure 10～15MPa, hydrogen to oil volume ratio 800～1500, volume space velocity 0.8～2.0h during liquid
-1
The invention has the beneficial effects as follows: contain composite molecular screen-modified Y molecular sieve and modified ZSM-5-23 molecular sieves in catalyst, Y molecular sieve, through the modification dealuminzation, improves its skeleton Si/Al and causes structure cell contraction, the reduction of surface acid center concentration, acid site strength increase, acid site distribution to disperse, produce simultaneously abundant secondary mesopore; Make heat and hydrothermal stability just strengthen; Hydrophobicity strengthens; Part of hydroxyl is removed, and sour density and acid strength change; Improve the adsorption and desorption performance of molecular sieve; Thereby make catalyst obtain higher catalytic pyrolysis performance.ZSM-23 molecular screen duct after modification is unobstructed, and the acid site number is few, and the isomery performance is outstanding, and light naphthar component isomery improves its octane number.In the present invention, composite molecular screen-modified Y molecular sieve and modified ZSM-5-23 molecular sieves mix and use with the disclosed formula rate of this invention, can take into account lytic activity and isomery performance, make the catalyst that finally makes reach optimal catalytic effect.
The specific embodiment
The specific embodiment of the present invention is as follows:
Embodiment 1:
(1) with commercially available NaY molecular sieve (relative crystallinity 90%, lattice constant 2.470nm, SiO
2/ Al
2O
3Mol ratio is 5.1, Na
2O content is 10.9wt%, and following examples are identical with comparative example) being 2.0mol/L with concentration, ammonium nitrate solution mixes, and solvent and solute weight ratio is 10, is warming up to 95 ℃, under agitation carry out ion-exchange 1.5 hours, elimination mother liquor, repeated exchanged 1 time, filter, washing, obtain Na
2O content is the NH of 2.9wt%
4The NaY sieve sample;
(2) take 500 grams (butt) NH
4The NaY molecular sieve is put into three-necked bottle, adds 1M NH
4NO
32.5 rise, stir and be warming up to 98 ℃, then take the speed of 7.25ml/ minute with the (NH of concentration as 1.0M
4)
2SiF
6Aqueous solution 870ml adds in three-necked bottle, finishes and continues stirring reaction 1 hour.Then stop stirring, standing 10 minutes, isolate the molecular sieve pulp on three-necked bottle top with decantation, suction filtration, washing, filter cake is dried to moisture content 20% at 110 ℃;
(3) dried sieve sample is placed in the hydrothermal treatment consists stove, 560 ℃ of control system temperature, water vapour pressure 0.10MPa, hydrothermal treatment consists 2.5 hours;
(4) sieve sample after hydrothermal treatment consists exchanges 1 hour with 1.5N ammonium nitrate solution 5 liters (with nitric acid, transferring to pH=3.0) under 92 ℃, repeated exchanged 1 time, and slurries suction filtration, washing, drying obtain modified Y molecular sieve A1, and physico-chemical property is listed in table 1.
Embodiment 2:
Get commercially available NaY molecular sieve 100 grams and exchange 1.5 hours under 90 ℃, elimination mother liquor, repeated exchanged 1 time with the ammonium nitrate solution 800ml of 1.5N, filter cake washs with deionized water, put back to the ammonium nitrate solution 800ml making beating of using again 1.5N in swap tank, be warming up to 95 ℃, with (the NH of 1.2M
4)
2SiF
6Aqueous solution 150ml evenly in 1.5 hours add swap tank, then continues reaction 1.5 hours, stops stirring, and standing 5 minutes, derive upper-class elements' screening the pulp liquid, suction filtration, wash, be dried to moisture content 15%; Sample is placed in the hydrothermal treatment consists stove, 580 ℃ of control system temperature, water vapour pressure 0.08MPa, hydrothermal treatment consists 2.0 hours; Sample exchanges 1.5 hours with 1.0N ammonium chloride solution 0.8 liter (with hydrochloric acid, transferring to pH=2.8) under 95 ℃, repeated exchanged 2 times, and slurries suction filtration, washing, drying obtain modified Y molecular sieve B1, and physico-chemical property is listed in table 1.
Embodiment 3:
Get SiO
2/ Al
2O
3Mol ratio is that 60 HZSM-23 molecular sieve 300g is placed in the hydrothermal treatment consists stove, 500 ℃ of control system temperature, and water vapour pressure 0.05MPa, hydrothermal treatment consists obtained modified ZSM-5-23 molecular sieve-4 A 2 in 1.0 hours, and physico-chemical property is listed in table 1.
Embodiment 4:
Get SiO
2/ Al
2O
3Mol ratio is that 70 HZSM-23 molecular sieve 200g is placed in the hydrothermal treatment consists stove, 460 ℃ of control system temperature, and water vapour pressure 0.08MPa, hydrothermal treatment consists obtained modified ZSM-5-23 molecular sieve B2 in 1.5 hours, and physico-chemical property is listed in table 1.
Comparative example 1:
Get commercially available LZ-210 and make modified Y molecular sieve sample C.Its physico-chemical property is in Table 1.
Comparative example 2:
Take 500 gram NH
4The NaY molecular sieve is put into there-necked flask, adds 2.5 liters of distilled water, is heated to 95 ℃ under stirring condition, drips 1.0M hexafluorosilicic acid aqueous ammonium 870ml in 2 hours with uniform speed, adds rear slurry and continues to stir 2 hours under 95 ℃.Stop stirring, isolate the molecular sieve on top with decantation after static 10 minutes, suction filtration, washing, drying, obtain modified Y molecular sieve sample D, and physico-chemical property is listed in table 1.
The physico-chemical property of table 1 modified molecular screen
Embodiment 5:
With modified Y molecular sieve A1225 gram, modified ZSM-5-23 molecular sieve-4 A 225 grams and adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) 167 grams are placed in the roller mixed grind, be pressed into paste, extruded moulding, and 105 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, then with the mixed solution dipping of tungstenic nickel, 110 ℃ of dryings 4 hours, then 500 ℃ of roastings 2 hours, obtain catalyst CA, its physico-chemical property is in Table 2.
Embodiment 6:
With modified Y molecular sieve B1200 gram, modified ZSM-5-23 molecular sieve B250 gram and adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) 200 grams are placed in the roller mixed grind, be pressed into paste, extruded moulding, and 105 ℃ of dryings 3 hours, then 500 ℃ of roastings 4 hours, then with the mixed solution dipping of tungstenic nickel, 110 ℃ of dryings 4 hours, then 500 ℃ of roastings 2 hours, obtain catalyst CB, its physico-chemical property is in Table 2.
Comparative example 3 and 4:
Change the composite molecular screen of the modification of example 5 (Y+ZSM-23) into the sample C of comparative example 1 and the sample D of comparative example 2, the addition of sample C and sample D is 250 grams, the preparation method makes the catalyst CC of comparative example 3 and the catalyst CD of comparative example 4 with embodiment 5, and its physico-chemical property is in Table 2.
Comparative example 5:
Make hydrocracking catalyst CE by CN1174756A embodiment 3, its physico-chemical property is in Table 2.
The physico-chemical property of table 2 catalyst
Embodiment 6
Catalyst performance evaluation adopts one-stage serial once by technological process, take vacuum distillate as raw material, feedstock oil character is in Table 3, feedstock oil is the nitrogenous control＜10ppm of effluent oil after an anti-refining stage is refining, reaction pressure is 14.7MPa, hydrogen to oil volume ratio 1500:1, cracking zone volume space velocity are 1.5h
-1The small-sized evaluating apparatus of hydrocracking is estimated the activity of hydrocracking catalyst CA, CB, CC, CD under these conditions.Evaluation result is listed in table 4.
Table 3 feedstock oil character
| Project | Analysis result |
| Density (20 ℃), g/cm 3 | 0.8906 |
| Sulphur, w% | 0.54 |
| Nitrogen, w% | 0.11 |
| Boiling range, ℃ | ? |
| Initial boiling point/10%/30%/50%/70%/90%/do | 298/364/405/431/458/509/551 |
Table 4 evaluating catalyst result
| The catalyst numbering | CA | CB | CC | CD | CE |
| One anti-effluent oil is nitrogenous, and * 10 -4w% | <10 | <10 | <10 | <10 | <10 |
| Reaction temperature, ℃ | 369 | 371 | 374 | 376 | 368 |
| ＜185 ℃ of cut yields, v%* | 59.5 | 60.3 | 57.8 | 58.4 | 59.0 |
| ＜65 ℃ of light naphthar octane numbers, RON | 82.2 | 84.6 | 79.1 | 78.3 | 78.5 |
* engler's fractionation result
Find out from evaluation result, hydrocracking catalyst CA of the present invention, CB activity are better than reference agent CC, CD, CE;＜65 ℃ of light naphthar octane numbers (RON) improve 3～5.5.
Claims (14)
1. light oil type hydrogen cracking catalyst that contains composite molecular screen, comprise composite molecular screen and the carrier of aperture aluminium oxide formation and the hydrogenation activity component of group VIB metal and group VIII metal composition that modified Y molecular sieve and modified ZSM-5-23 molecular sieves form, it is characterized in that: described composite molecular screen comprises modified Y molecular sieve and modified ZSM-5-23 molecular sieve, the SiO of described modified Y molecular sieve
2/ Al
2O
3Mol ratio is 10 ~ 15, specific area 700 ~ 850m
2/ g, pore volume 0.40 ~ 0.50ml/g, lattice constant 2.445 ~ 2.455nm, relative crystallinity 〉=90%, Na
2O content≤0.15wt%, infrared total acid are 0.5 ~ 1.2mmol/g; The SiO of described modified ZSM-5-23 molecular sieve
2/ Al
2O
3Mol ratio is 50 ~ 70, specific area 260 ~ 450m
2/ g, pore volume 0.30 ~ 0.45ml/g, infrared total acid is generally 0.1 ~ 0.25mmol/g.
2. the light oil type hydrogen cracking catalyst that contains composite molecular screen according to claim 1, it is characterized in that: in described composite molecular screen, the weight ratio of modified Y molecular sieve and modified ZSM-5-23 molecular sieves is 75:25 ~ 95:5.
3. the light oil type hydrogen cracking catalyst that contains composite molecular screen according to claim 1, it is characterized in that: described little porous aluminum oxide is boehmite, and its pore volume is 0.45 ~ 0.55ml/g, and specific area is 180 ~ 380m
2/ g.
4. the light oil type hydrogen cracking catalyst that contains composite molecular screen according to claim 1, it is characterized in that: described group VIB metal is tungsten or molybdenum, group VIII metal is nickel or cobalt.
5. the light oil type hydrogen cracking catalyst that contains composite molecular screen according to claim 1, it is characterized in that: described composite molecular screen content is 30 ~ 60wt%, aperture aluminium oxide 10 ~ 26wt% group VIB metal is take oxide content as 20 ~ 26wt%, and group VIII metal is take the content of oxide as 3 ~ 7wt%.
6. the described preparation method who contains the light oil type hydrogen cracking catalyst of composite molecular screen of according to claim 1-5 any one, is characterized in that, comprises the following steps:
With composite molecular screen and the adhesive that made by little porous aluminum oxide and dilute nitric acid solution peptization carry out mechanical mixture, roll, moulding, then dry, roasting, obtain catalyst carrier, carrier floods with the maceration extract that contains group VIB metal and group VIII metal, then dry, roasting, make finished catalyst.
7. the preparation method who contains the light oil type hydrogen cracking catalyst of composite molecular screen according to claim 6, is characterized in that, in described composite molecular screen, modified Y molecular sieve is to make by the following method:
Sodium type Y molecular sieve carries out ion-exchange with the aqueous solution of ammonium salt, prepares Na content with Na
2O weighing scale content is less than 3.0% ammonium type Y molecular sieve;
Ammonium type Y molecular sieve hexafluorosilicic acid ammonium salt solution dealumination complement silicon, the silica alumina ratio of raising molecular sieve, the sieve sample after dealumination complement silicon separates with accessory substance, and sieve sample is carried out suction filtration, washing and dry;
Sieve sample to drying carries out hydrothermal treatment consists;
Sieve sample after hydrothermal treatment consists exchanges with ammonium salt solution, and ammonium salt solution transfers to pH=2.5 ~ 5.5 with acid.
8. the preparation method who contains the light oil type hydrogen cracking catalyst of composite molecular screen according to claim 7, it is characterized in that, described reaction condition with hexafluorosilicic acid ammonium salt solution dealumination complement silicon is: the concentration of described hexafluorosilicic acid ammonium salt solution is 0.5 ~ 1.2M, system temperature is controlled at 70 ~ 120 ℃, and the dealumination complement silicon time is 0.3 ~ 5.0 hour.
9. the preparation method who contains the light oil type hydrogen cracking catalyst of composite molecular screen according to claim 7, it is characterized in that: described sieve sample and separation of by-products adopt sedimentation-separation technology to isolate zeolite product and accessory substance, and the sedimentation time is 0.1 ~ 1.0 hour.
10. the preparation method who contains the light oil type hydrogen cracking catalyst of composite molecular screen according to claim 7, is characterized in that: 500 ~ 750 ℃ of the temperature of described Y molecular sieve hydrothermal treatment consists, water vapour pressure 0.01 ~ 0.50MPa, 0.5 ~ 5.0 hour time.
11. the preparation method who contains the light oil type hydrogen cracking catalyst of composite molecular screen according to claim 7, it is characterized in that: the sieve sample after described hydrothermal treatment consists is with in the ammonium salt solution exchange step, ammonium salt is one or several in ammonium chloride, ammonium nitrate, ammonium sulfate, and the acid of regulating pH is hydrochloric acid, nitric acid or sulfuric acid.
12. the preparation method who contains the light oil type hydrogen cracking catalyst of composite molecular screen according to claim 6, it is characterized in that, in described composite molecular screen, the condition of described HZSM-23 zeolite-water heat treatment is: 400 ~ 600 ℃ of temperature, water vapour pressure 0.01 ~ 0.20MPa, 0.5 ~ 3.0 hour time.
13. the described application that contains the light oil type hydrogen cracking catalyst of composite molecular screen of according to claim 1-5 any one is characterized in that: in hydrocracking process, be used for the hydrocracking process of voluminous light ends oil.
14. the described application that contains the light oil type hydrogen cracking catalyst of composite molecular screen of according to claim 1-5 any one, it is characterized in that, reaction process condition is: reaction temperature is 360 ~ 380 ℃, stagnation pressure 10 ~ 15MPa, hydrogen to oil volume ratio 800 ~ 1500, volume space velocity 0.8 ~ 2.0h during liquid
-1
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